US5480984A - Process of preparing high solids low viscosity polysaccharides - Google Patents
Process of preparing high solids low viscosity polysaccharides Download PDFInfo
- Publication number
- US5480984A US5480984A US07/834,163 US83416392A US5480984A US 5480984 A US5480984 A US 5480984A US 83416392 A US83416392 A US 83416392A US 5480984 A US5480984 A US 5480984A
- Authority
- US
- United States
- Prior art keywords
- guar
- hydrophobically modified
- polysaccharide
- oxidizing agent
- hydrogen peroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
Definitions
- the invention relates to water soluble polymers.
- the invention relates to oxidatively-degraded polysaccharides useful as fluid additives.
- Polysaccharides such as cellulose ethers and guar gum, etc., are known in a wide variety of applications for food, cosmetics, pharmaceuticals, oil drilling, coatings, construction, graphic arts, etc. Because these naturally occurring polymers have high molecular weights, it has often been desirable to employ a oxidative treatment to degrade the polymer. Degradative polysaccharide treatments and low viscosity polymers are described in Canadian Patent 839,258, British Patent specification 1,139,637 and U.S. Pat. Nos. 4,316,982; 4,838,944; 4,874,854; and 4,894,448.
- An aqueous polysaccharide composition is characterized in that the composition has a solids content greater than 5% by weight and a viscosity at 25° C. below 9500 mPa.s, where the polysaccharide composition contains at least one polysaccharide selected from the group of hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), water soluble ethylhydroxyethylcellulose (EHEC), carboxymethylhydroxyethylcellulose (CMHEC), hydroxypropylhydroxyethylcellulose (HPHEC), methylcellulose (MC), methylhydroxypropylcellulose (MHPC), methylhydroxyethylcellulose (MHEC), carboxymethylmethylcellulose (CMMC), guar, carboxymethyl guar (CM guar), hydroxyethyl guar (HE guar), hydroxypropyl guar (HP guar), carboxymethylhydroxypropyl guar (CMHP guar), carboxymethylhydroxypropyl guar
- the invention provides a simple and efficient process for producing a high solids, low viscosity aqueous polysaccharide product with a percent solids greater than 5% and a Brookfield viscosity at 25° C. below 9500 mPa.s comprising the steps:
- a preferred process for producing a high solids low viscosity aqueous polysaccharide composition comprises the steps:
- the preferred aqueous polysaccharides are carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), water soluble ethylhydroxyethylcellulose (EHEC), carboxymethylhydroxyethylcellulose (CMHEC), hydroxypropylhydroxyethylcellulose (HPHEC), methylcellulose (MC), methylhydroxypropylcellulose (MHPC), methylhydroxyethylcellulose (MHEC), carboxymethylmethylcellulose (CMMC), guar, carboxymethyl guar (CM guar), hydroxyethylguar (HE guar), methylhydroxypropylguar (MHP guar), hydroxypropylguar (HP guar), carboxymethylhydroxypropylguar (CMHP guar), cationic guar, hydrophobically modified hydroxyethylcellulose (HMHEC) or hydrophobically modified ethylhydroxyethylcellulose (HMEHEC).
- CMC carb
- Guar and modified polysaccharides useful for the practice of the present invention are well known in the art and are commercially available as solids, solutions and suspensions. But in spite of a need which could not be met by conventional oxidatively degraded polysaccharides, it remained for the present invention to satisfy that need.
- hydrogen peroxide is the preferred oxidizing agent
- any equivalent oxidizing agent could be substituted which could similarly degrade the modified polysaccharide to the same solids content and viscosity level.
- An advantage provided by hydrogen peroxide used without a metal catalyst is that food and pharmaceutical grade materials may be produced starting with higher viscosity food or pharmaceutical grade polysaccharides. Although it is certainly possible to degrade the polysaccharides using other than 30-50% hydrogen peroxide, the added water would have to be adjusted to ultimately obtain the high solids, low viscosity compositions of the invention.
- the amount of hydrogen peroxide required for depolymerization has been found to vary according to the polysaccharide.
- a generalized process for producing a high solids low viscosity aqueous polysaccharide composition comprises the steps.
- a particularly useful application for this generalized process involves the use of CMC, HPC or guar as the polysaccharide where 50% hydrogen peroxide is used in step (1).
- This process may be continuous, incremental or batchwise.
- the modified polysaccharide need not be a single material or necessarily the same in each step.
- CMC could be added in steps (3) and (4) and HEC could be added in steps (5) and (6) to produce a high solids, low viscosity mixture of CMC and HEC.
- Hydrogen peroxide is the preferred oxidant for the practice of the invention, but other oxidants can be used as long as they similarly depolymerize the polysaccharide without producing objectionable by-products.
- Commercially available 50% hydrogen peroxide is particularly suitable when water addition must be kept as low as possible.
- Carboxymethylcellulose was prepared in aqueous isopropanol and purified with aqueous methanol. It was then dried and granulated.
- a reactor was cleaned and dried and 545 kg of water was added and heated to 80° C. Agitation was set at 130 rpm. Then 3.5 kg 50% hydrogen peroxide was added followed by 68 kg of CMC which was added in about 45 minutes. The reaction proceeded for 75 minutes after completion of the CMC addition.
- Example 1 The procedure of Example 1 was repeated except that CMC with different levels of substitution ranging from 0.2 to 1.2 was used as the starting material. Products were produced in all cases with percent solids ranging up to about 50% along with a 25° C. Brookfield viscosity of 9400 mPa.s or less.
- Example 1 The procedure of Example 1 was repeated except that the starting material was selected from guar, carboxymethylhydroxyethylcellulose (CMHEC), hydrophobically modified hydroxyethylcellulose (HMHEC) (available from the Aqualon Company as Natrosol® Plus), methylhydroxypropylcellulose (MHPC), hydroxyethylcellulose(HEC), carboxymethylguar (CM guar), hydroxypropylguar (HP guar) and carboxymethylhydroxypropylguar (CMHP guar). Amounts of hydrogen peroxide and polysaccharide were varied to give percent solids ranging from 10 to 50%. Corresponding viscosities of from 44 to 7800 were obtained.
- CCMHEC carboxymethylhydroxyethylcellulose
- HHEC hydrophobically modified hydroxyethylcellulose
- HP guar hydroxypropylguar
- CMHP guar carboxymethylhydroxypropylguar
- a 703 g portion of 50% hydrogen peroxide was added to 23.5 kg water which was constantly stirred. After heating to 80° C., 10.9 kg, hydroxyethylcellulose (HEC) was added over a 30 minute period. Reaction was carried out at 90°-95° C. for about 7 hours. The reaction mixture was cooled to 70° C. and 52 g of methyl parasept was added as a preservative. A 30% solids composition was obtained with a Brookfield viscosity at 25° C. of 1000 mPa.s. Very high intermediate viscosities, 1-2 MM mPa.s, were observed, such that powerful agitation was required.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Jellies, Jams, And Syrups (AREA)
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Grain Derivatives (AREA)
Abstract
Description
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/834,163 US5480984A (en) | 1990-07-02 | 1992-02-11 | Process of preparing high solids low viscosity polysaccharides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US54686690A | 1990-07-02 | 1990-07-02 | |
US07/834,163 US5480984A (en) | 1990-07-02 | 1992-02-11 | Process of preparing high solids low viscosity polysaccharides |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US54686690A Division | 1990-07-02 | 1990-07-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
US5480984A true US5480984A (en) | 1996-01-02 |
Family
ID=24182358
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/834,163 Expired - Lifetime US5480984A (en) | 1990-07-02 | 1992-02-11 | Process of preparing high solids low viscosity polysaccharides |
US08/006,025 Expired - Fee Related US6054511A (en) | 1990-07-02 | 1993-01-15 | High solids low viscosity polysaccharides |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/006,025 Expired - Fee Related US6054511A (en) | 1990-07-02 | 1993-01-15 | High solids low viscosity polysaccharides |
Country Status (7)
Country | Link |
---|---|
US (2) | US5480984A (en) |
EP (1) | EP0465992B1 (en) |
JP (1) | JPH089680B2 (en) |
AT (1) | ATE167488T1 (en) |
AU (1) | AU650273B2 (en) |
CA (1) | CA2046089C (en) |
DE (1) | DE69129608T2 (en) |
Cited By (17)
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US5741482A (en) * | 1996-11-06 | 1998-04-21 | Hercules Incorporated | Air treatment gel compositions |
US5804166A (en) * | 1997-05-09 | 1998-09-08 | Hercules Incorporated | Low VOC hair sprays containing cellulose ethers |
US5990052A (en) * | 1994-09-02 | 1999-11-23 | Halliburton Energy Services, Inc. | Foamed fracturing fluid |
WO2000032636A1 (en) * | 1998-11-27 | 2000-06-08 | Wolff Walsrode Aktiengesellschaft | Method for the production of low-viscous water-soluble cellulose ethers |
US20030045708A1 (en) * | 2001-06-11 | 2003-03-06 | Jesse Magallanes | Galactomannan compositions and methods for making and using same |
WO2004091557A2 (en) * | 2003-04-09 | 2004-10-28 | Hercules Incorporated | Cationic, oxidized polysaccharides in conditioning applications |
US20050227902A1 (en) * | 2004-04-08 | 2005-10-13 | Paquita Erazo-Majewicz | Cationic, oxidized polysaccharides in conditioning applications |
US20070244204A1 (en) * | 2006-04-13 | 2007-10-18 | Evelyne Prat | Rheology enhancers in non-oilfield applications |
US20090054639A1 (en) * | 2006-02-24 | 2009-02-26 | Solvay (Societe Anonyme) | Process for the Manufacture of Oxidized Starch, Oxidized Starch and Its Use |
US20140165877A1 (en) * | 2011-04-01 | 2014-06-19 | Patrick A.C. Gane | Self-binding pigment hybrid |
US9512237B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Method for inhibiting the growth of microbes with a modified cellulose fiber |
US9512563B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Surface treated modified cellulose from chemical kraft fiber and methods of making and using same |
US9512561B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
US9511167B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
US9951470B2 (en) | 2013-03-15 | 2018-04-24 | Gp Cellulose Gmbh | Low viscosity kraft fiber having an enhanced carboxyl content and methods of making and using the same |
US9976097B2 (en) | 2015-03-04 | 2018-05-22 | InnoVerdant, LLC | Charcoal ignition fluid |
CN109336983A (en) * | 2018-11-15 | 2019-02-15 | 泸州北方纤维素有限公司 | Preparation method for extra low viscose hydroxyethyl cellulose |
Families Citing this family (30)
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---|---|---|---|---|
ATE192335T1 (en) * | 1990-12-20 | 2000-05-15 | Warner Jenkinson Co Inc | MOIST POWDER FILM-FORMING COMPOSITIONS |
DE4137237A1 (en) * | 1991-11-13 | 1993-05-19 | Gruenau Gmbh Chem Fab | CONTINUOUS METHOD FOR DEGRADING HETEROPOLYSACCHARIDES |
EP0566911B1 (en) * | 1992-04-20 | 1998-08-26 | Aqualon Company | Improved leveling aqueous coating compositions |
FR2716928B1 (en) * | 1994-03-03 | 1996-05-03 | Inst Francais Du Petrole | Water-based process and fluid using hydrophobically modified cellulosic derivatives as a filtrate reducer. |
DE4411681A1 (en) * | 1994-04-05 | 1995-10-12 | Hoechst Ag | Process for the preparation of low molecular weight polysaccharide ethers |
FR2719601B1 (en) * | 1994-05-04 | 1996-06-28 | Inst Francais Du Petrole | Water-based process and fluid for controlling the dispersion of solids. Application to drilling. |
EP0884330A1 (en) | 1997-06-12 | 1998-12-16 | Meyhall AG | Process for producing pure guar seed flour |
FR2802932A1 (en) * | 1999-12-27 | 2001-06-29 | Rhodia Food S A S | Galactomannan oligomers obtained by depolymerization, subjecting the solid galactomannan, especially guar gum, a solvent system and an oxidant to elevated temperature and pressure |
JP2004506057A (en) * | 2000-08-03 | 2004-02-26 | ハーキュリーズ・インコーポレーテッド | Process for producing chemically or enzymatically modified polysaccharides and products produced thereby |
US7259192B2 (en) * | 2002-06-25 | 2007-08-21 | Rhodia, Inc. | Molecular weight reduction of polysaccharides by electron beams |
US20050209449A1 (en) * | 2002-07-10 | 2005-09-22 | Akzo Nobel N.V. | Depolymerization of water soluble polysaccharides |
JP2005537347A (en) * | 2002-07-26 | 2005-12-08 | エフ エム シー コーポレーション | Production of microcrystalline cellulose |
ITVA20030025A1 (en) * | 2003-07-17 | 2005-01-18 | Lamberti Spa | ENZYMATIC DEPOLYMERIZATION OF CARBOSSIMETHYL CELLULOSE AND RELATED PRODUCTS. |
US7174960B2 (en) | 2004-03-05 | 2007-02-13 | Halliburton Energy Services, Inc. | Method to depolymerize as well as derivatize a polysaccharide in a hydrocarbon slurry |
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WO2009117073A1 (en) * | 2008-03-15 | 2009-09-24 | Hercules Incorporated | Clay slurries and use thereof in pulp and papermaking applications |
FR2958648B1 (en) * | 2010-04-09 | 2015-10-30 | Greentech | NOVEL OLIGOSACCHARIDE COMPOUNDS AND USE AS ENERGY AGENT |
WO2011124861A2 (en) * | 2010-04-09 | 2011-10-13 | Greentech | Use of xanthan-derived oligosaccharide compounds as energizing agent |
IT1400340B1 (en) | 2010-05-25 | 2013-05-24 | Lamberti Spa | METHOD FOR SEALING PODS. |
US8524042B2 (en) | 2010-08-23 | 2013-09-03 | Hercules Incorporated | Method of treating paper forming wire surface |
ITVA20110028A1 (en) | 2011-10-03 | 2013-04-04 | Lamberti Spa | DEPOLYMERIZATION OF POLYSACCHARIDES AND RELATED PRODUCTS |
BR112014031471B1 (en) * | 2012-07-17 | 2020-12-01 | Dow Global Technologies Llc | liquid composition, use of liquid composition, solid dispersion, process for producing the solid dispersion and process for coating a dosage form |
KR101971738B1 (en) * | 2012-12-11 | 2019-04-23 | 롯데정밀화학 주식회사 | Method for Preparation of Very Low Viscosity Hydroxylalkyl Cellulose with Partial Neutralization |
FR3012752B1 (en) | 2013-11-04 | 2015-11-20 | Coatex Sas | USE OF DEPOLYMERIZED CARBOXYL CELLULOSES FOR THE DISPERSION AND MILLING OF MINERAL MATERIALS |
US9464227B2 (en) | 2014-03-24 | 2016-10-11 | Lamberti Spa | Moisturizing agents |
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US20220185733A1 (en) * | 2020-12-11 | 2022-06-16 | Sika Technology Ag | Cementitious compositions comprising oxidatively degraded polysaccharide as water reducing agents |
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- 1991-07-02 CA CA002046089A patent/CA2046089C/en not_active Expired - Fee Related
- 1991-07-02 DE DE69129608T patent/DE69129608T2/en not_active Expired - Fee Related
- 1991-07-02 AT AT91110943T patent/ATE167488T1/en active
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- 1991-07-05 AU AU80231/91A patent/AU650273B2/en not_active Ceased
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1993
- 1993-01-15 US US08/006,025 patent/US6054511A/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
AU650273B2 (en) | 1994-06-16 |
EP0465992A1 (en) | 1992-01-15 |
DE69129608D1 (en) | 1998-07-23 |
DE69129608T2 (en) | 1998-10-15 |
EP0465992B1 (en) | 1998-06-17 |
CA2046089A1 (en) | 1992-01-03 |
JPH089680B2 (en) | 1996-01-31 |
CA2046089C (en) | 2003-12-30 |
US6054511A (en) | 2000-04-25 |
ATE167488T1 (en) | 1998-07-15 |
AU8023191A (en) | 1992-01-16 |
JPH04306245A (en) | 1992-10-29 |
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